Solid-acid isomerization catalyst and process

Abstract

A catalyst and process is disclosed to selectively upgrade a paraffinic feedstock to obtain an isoparaffin-rich product for blending into gasoline. The catalyst comprises a support of a sulfated oxide or hydroxide of a Group IVB (IUPAC 4) metal, a first component comprising at least one Group III A (IUPAC 13) component, and at least one platinum-group metal component which is preferably platinum.

1. A catalyst consisting essentially of a support comprising a sulfated oxide or hydroxide of at least one of the elements of Group IVB (IUPAC 4), the support having deposited thereon; a first component comprising at least one Group III A (IUPAC 13) component; a second component comprising at least one platinum-group metal component; and optionally a third component selected from the group consisting of iron, cobalt, nickel, rhenium, europium, terbium, holmium, erbium, thulium, ytterbium, yttrium, and combinations thereof. 
     
     
       2. The catalyst of  claim 1  wherein the first component comprises from about 0.01 to about 10 mass-%, on an elemental basis, of the catalyst. 
     
     
       3. The catalyst of  claim 1  wherein the second component comprises from about 0.01 to about 2 mass-%, on an elemental basis, of the catalyst. 
     
     
       4. The catalyst of  claim 1  wherein the element of Group IVB (IUPAC 4) comprises zirconium. 
     
     
       5. The catalyst of  claim 1  wherein the catalyst comprises from about 0.5 to about 5 mass-% sulfur on an elemental basis. 
     
     
       6. The catalyst of  claim 1  wherein the atomic ratio of the first component to the second component is at least about 2. 
     
     
       7. The catalyst of  claim 1  further comprising from about 2 to about 25 mass-% of a refractory inorganic-oxide binder. 
     
     
       8. The catalyst of  claim 7  wherein the refractory inorganic-oxide binder comprises alumina. 
     
     
       9. The catalyst of  claim 1  wherein the first component consists essentially of one single Group III A (IUPAC 13) component and the second component consists essentially of one single metal selected from the platinum-group metals. 
     
     
       10. The catalyst of  claim 1  wherein the first component is selected from the group consisting of gallium, indium, and the combination thereof. 
     
     
       11. The catalyst of  claim 1  wherein the second component is platinum. 
     
     
       12. The catalyst of  claim 1  wherein the third component comprises from about 0.1 to about 5 wt-%, on an elemental basis, of the catalyst. 
     
     
       13. A hydrocarbon conversion catalyst consisting essentially of a support comprising a sulfated oxide or hydroxide of zirconium having deposited thereon; from about 0.01 to about 10 mass-%, on an elemental basis, of a Group III A (IUPAC 13) component selected from the group consisting of gallium, indium, and mixtures thereof; from about 0.01 to about 2 mass-%, on an elemental basis, of a platinum component; and optionally, from about 0.1 to about 5 mass-% of a third component selected from the group consisting of iron, cobalt, nickel, rhenium, europium, terbium, holmium, erbium, thulium, ytterbium, yttrium, and combinations thereof. 
     
     
       14. A process for the preparation of a catalyst suitable for hydrocarbon conversion consisting essentially of a sulfated support comprising at least one of the oxides and hydroxides of the elements of Group IVB (IUPAC 4), a first component comprising at least one Group III A (IUPAC 13) components, a second component comprising at least one platinum-group metal, and optionally a third component selected from the group consisting of iron, cobalt, nickel, rhenium, europium, terbium, holmium, erbium, thulium, ytterbium, yttrium, and combinations thereof, the process comprising sulfating an oxide or hydroxide of at least one element of Group IVB (IUPAC 4) to form a sulfated support; depositing on the sulfated support, the first component; depositing on the sulfated support, the second component; and optionally depositing on the sulfated support, the third component to form said catalyst. 
     
     
       15. A process for converting hydrocarbons by contacting a feed with a solid acid catalyst to give a converted product, the catalyst consisting essentially of a support comprising a sulfated oxide or hydroxide of at least an element of Group IVB (IUPAC 4), a first component comprising at least one Group III A (IUPAC 13) component, a second component comprising at least one platinum-group metal, and optionally a third component selected from the group consisting of iron, cobalt, nickel, rhenium, europium, terbium, holmium, erbium, thulium, ytterbium, yttrium, and combinations thereof. 
     
     
       16. The process of  claim 15  wherein the hydrocarbon conversion process is selected from the group consisting of cracking, hydrocracking, aromatic alkylation, isoparaffin alkylation, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation, ring opening, and syngas shift. 
     
     
       17. A process for the isomerization of a paraffinic feedstock to obtain a product having an increased isoparaffin content comprising contacting the paraffinic feedstock in an isomerization zone maintained at isomerization conditions comprising a temperature from about 40 to about 250° C., a pressure from about 100 kPa to about 10 MPa and a liquid hourly space velocity from about 0.2 to about 25 hr −1  with a solid acid isomerization catalyst consisting essentially of a sulfated support comprising an oxide or hydroxide of elements of Group IVB (IUPAC 4), a first component comprising at least one Group III A (IUPAC 13) component, a second component comprising at least one platinum-group metal, and optionally a third component selected from the group consisting of iron, cobalt, nickel, rhenium, europium, terbium, holmium, erbium, thulium, ytterbium, yttrium, and combinations thereof, and recovering an isoparaffin-rich product. 
     
     
       18. The process of  claim 17  wherein free hydrogen is present in the isomerization zone in an amount from about 0.01 to about 20 moles per mole of C 5 + hydrocarbons present in the zone. 
     
     
       19. The process of  claim 17  wherein the isomerization conditions comprise a temperature from about 100 to about 200° C., a pressure from about 300 kPa to about 4 MPa, and a liquid hourly space velocity from about 0.5 to about 15 hr −1 , and wherein free hydrogen is present in the isomerization zone in an amount from about 0.05 to about 5 moles per mole of C 5 + hydrocarbons present in the zone. 
     
     
       20. The process of  claim 17  wherein the isomerization catalyst further comprises a refractory inorganic-oxide binder. 
     
     
       21. The process of  claim 20  wherein the refractory inorganic-oxide binder comprises alumina. 
     
     
       22. The process of  claim 17  wherein the atomic ratio of the first component to the second component is at least about 2. 
     
     
       23. The process of  claim 17  wherein the first component is selected from the group consisting of gallium, indium, or mixtures thereof and the second component is platinum. 
     
     
       24. The process of  claim 17  wherein the third component comprises from about 1 to about 5 wt. % on an elemental basis, of the catalyst. 
     
     
       25. The process of  claim 17  further comprising using at least a portion of the isoparaffin-rich product to blend a gasoline product.